Herein, a pH-independent interpenetrating polymeric networks (Fe-SA-C) were fabricated from graphitic biochar (BC) and iron-alginate hydrogel (Fe-SA) for removal of Cr(VI) and Pb(II) in aqueous solution. Fourier transform infrared spectroscopy (FTIR), Raman spectroscopy and scanning electron microscope (SEM) results demonstrated that graphitic BC interpenetration increased surface porosity and distorted surfaces of Fe-SA, which boosted availability of hydroxyl (-OH) group. Fe³⁺ as a cross-linking agent of the alginate endowed Fe-SA-C with positive surfaces (positive zeta potential) and excellent pH buffering capacity, while excessive Fe³⁺ was soldered on Fe-SA-C matrix as FeO(OH) and Fe₂O₃. Cr(VI) removal at pH of 3 by Fe-SA-C (20.3 mg g⁻¹) were 30.3% and 410.6% greater than that by Fe-SA and BC, respectively. Fe-SA-C exhibited minor pH dependence over pH range of 2–7 towards Cr(VI) retention. Greater zeta potential of Fe-SA-C over Fe-SA conferred a better electrostatic attraction with Cr(VI). FTIR and XPS of spent sorbents confirmed the reduction accounted for 98.5% for Cr(VI) removal mainly due to participation of –OH. Cr(VI) reduction was further favored by conductive carbon matrix in Fe-SA-C, as evidenced by more negative Tafel corrosion potential. Reductively formed Cr(III) was subsequently complexed with carboxylic groups originating from oxidation of –OH. Thus, Cr(VI) removal invoked electrostatic attraction, reduction, and surface complexation mechanisms. Pb(II) removal with excellent pH independence was mainly ascribed to surface complexation and possible precipitation. Thus, the functionalized, conductive, and positively-charged Fe-SA-C extended its applicability for Cr(VI) and Pb(II) removal from aqueous solutions in a wide pH range. This research could expand the application of hydrogel materials for removal of both cationic and anionic heavy metals in solutions over an extended pH range.

It has been shown that chemical modification of chitosan with sulfur (S) functional groups could significantly enhance its chelating capability with heavy metals included Cd(II). However, a molecular level understanding has been lacking. Here, we carried out X-ray absorption fine structure (XAFS) and Fourier transformed infrared (FTIR) spectra studies to bridge this knowledge gap. The results indicate that both Cd–O/N and Cd–S bonds exist in the complex of Cd(II) with dithiocarbamate chitosan (DTC-CTS). S functional groups (dithiocarbamate) in DTC-CTS play the major role in complexation with Cd(II) and S content affects the adsorption mechanism. At low S content, Cd(II) is mainly adsorbed on DTC-CTS as an outer-sphere complex with two monodentate amino groups and two water molecules in tetrahedral configuration. At high S content, Cd adsorption dominantly occurs by formation of an inner-sphere complex with two bidentate mononuclear S ligands in tetrahedral configuration. This investigation provides information on the effectiveness and mechanisms of Cd(II) removal that is critical for evaluating modified chitosan applications for stabilization of Cd(II) in surface water, groundwater, soils and sediments.

It is highly desirable but remains extremely challenging to develop a facile strategy to prepare adsorbent for dealing with heavy metal pollution in water. Here, we report a facile approach for preparing sulfydryl-functionalized graphene oxide (S-GO) by cross-linking method with an unprecedented adsorption capacity and ultrahigh selectivity for efficient Hg(II) removal. The adsorbents exhibit a prominent performance in capturing Hg(II) from wastewater with a record-high adsorption capacity of 3490 mg/g and rapid kinetics to reduce Hg(II) contaminants below the discharge standard of drinking water (2 ppb) within 60 min under a wide pH range even in the coexistent of other interfering metal ions. In addition, the adsorbents can be also easily recycled and reused multiple times with no apparent decline in removal efficiency. Considering the broad diversity, we developed also a magnetic Fe₃O₄/S-GO adsorbent by a simple chemical cross-linking reaction to achieve rapid separation of S-GO from their aqueous solution. In addition, the adsorbents were successfully applied in dealing with the practical industrial wastewater. The results indicate the potential of rationally designed sulfydryl-functionalized graphene oxide for high performance Hg(II) removal.

Developing low-cost and high-performance biosorbent for water purification continues drawing more and more attention. In this study, cellulose-chitosan composite hydrogels were fabricated via a co-dissolution and regeneration process using a molten salt hydrate (a 60 wt% aqueous solution of LiBr) as a solvent. The addition of chitosan not only introduced functionality for metal adsorption but also increased the specific surface area and improved the mechanical strength of the composite hydrogel, compared to pure cellulose hydrogel. Batch adsorption experiments indicated that the composite hydrogel with 37% cellulose and 63% chitosan exhibited an adsorption capacity of 94.3 mg/g (1.49 mmol/g) toward Cu²⁺ at 23 °C, pH 5, and initial metal concentration of 1500 mg/L, which was 10 times greater than the adsorption capacity of pure cellulose hydrogel. Competitive adsorption from a mixed metals solution revealed that the cellulose-chitosan composite hydrogel exhibited selective adsorption of the metals in the order of Cu²⁺ > Zn²⁺ > Co²⁺. This study successfully demonstrated an innovative method to fabricate biosorbents from abundant and renewable natural polymers (cellulose and chitosan) for removing metal ions from water.

Presently, graphenic nanomaterials are being studied as candidates for wastewater pollutant removal. In this study, two graphite oxides produced from natural graphite with different grain sizes (325 and 10 mesh), their respective reduced graphene oxides and one reduced graphene oxide with nitrogen functional groups were synthesized and tested to remove a surfactant model substrate, Triton X-100, from an aqueous solution. Kinetic experiments were carried out and adjusted to pseudo-first order equation, pseudo-second order equation, Elovich, Chain-Clayton and intra-particle diffusion models. Reduced graphene oxides displayed an instantaneous adsorption due to their accessible and hydrophobic surfaces, while graphite oxides hindered the TX100 adsorption rate due to their highly superficial oxygen content. Results from the adsorption isotherms showed that the Sips model perfectly described the TX100 adsorption behavior of these materials. Higher adsorption capacities were developed with reduced graphene oxides, being maximum for the material produced from the lower graphite grain size (qₑ = 3.55·10⁻⁶ mol/m²), which could be explained by a higher surface area (600 m²/g), a lower amount of superficial oxygen (O/C = 0.04) and a more defected structure (ID/IG = 0.85). Additionally, three commercial high surface area graphites in the range of 100–500 m²/g were evaluated for comparison purposes. In this case, better adsorption results were obtained with a more graphitic material, HSAG100 (qₑ = 1.72·10⁻⁶ mol/m²). However, the best experimental results of this study were obtained using synthesized graphenic materials.

Absorption is an eminent technology for volatile organic compounds (VOCs) elimination with the merits of high efficiency and low cost. Absorbent plays a critical role in the absorption process, and the thermal stability, saturation capacity, and regeneration performance should be concerned. As a kind of green and eco-friendly solvent, ionic liquid (IL) is expected to be a substitute for the conventional VOCs absorbent. In this study, 1-butyl-3-methylimidazolium hexafluorophosphate ([Bmim][PF₆]) is employed to absorb the modeling VOCs (toluene and acetone). Moreover, the used [Bmim][PF₆] is recovered by thermal distillation and the reusability is then conducted by consecutive batch experiments. Based on that, the thermal stability of [Bmim][PF₆] is comprehensively examined, in which the kinetic and thermodynamic parameters are also calculated. Results reveal that [Bmim][PF₆] owned promising toluene absorption performance with inlet concentration of 3000 mg/m³ and flow rate of 300 mL/min at 20 °C, it possesses the saturated adsorption capacity of 5.16 mg/g. [Bmim][PF₆] also shows satisfying thermal stability up to 610 K. In addition, thermal distillation is proved to be a reliable regeneration route on account of the recovered [Bmim][PF₆] remained satisfying capacity even after five cycles.

One of the strategies to realize a nitrogen cycle society, we attempted to recover ammonium ions from industrial wastewater, especially sewage water with adsorbent materials. We have developed an adsorbent with high ammonium selectivity based on copper hexacyanoferrate and granulated it as pellets. Using a compact column system filled with this granule adsorbent, ammonium ions were recovered from sewage containing 1000–1500 mg-NH₄⁺/L ammonium ions. Despite the coexistence of many metal ions, the adsorbent selectively and stably adsorbed ammonium ions. Furthermore, it was shown that the saturated adsorbent can be regenerated by flowing a potassium ion solution through a column adsorbent to desorb ammonium ions. In other words, the column can be used repeatedly, and there was almost little deterioration in adsorption even after 250 cycles. In addition, it was shown that by increasing the number of stages of this column, it is possible to sufficiently reduce the ammonium in the adsorbent solution and recover the concentrated ammonium solution.

The removal of halogenated dye and sensing of pharmaceutical products in the water bodies with quick purification time is of high need due to the scarcity of drinking water. The present work reported on the preparation of graphitic carbon nitride (g-C₃N₄) for quick time water contaminant adsorption, followed by synthesizing silver nanoparticles decorated graphitic carbon nitride for pharmaceutical product sensing using in-situ SERS technique. The prepared graphitic carbon nitride is used to study the adsorption behavior of water contaminants at room temperature, in the presence of methylene blue (MB) as an adsorbate model. The water-soluble graphitic carbon nitride, even at low concentration, possesses an excellent ability to adsorb halogenated organic dye. As a result, the dyes are found to adsorb within ∼5s even without any additional physical or chemical activation. From the UV–Vis absorption investigations, it has been perceived that in the presence of graphitic carbon nitride (g-C₃N₄) the dye adsorption efficacy is observed nearly 80% with the well fitted linearly of R² = 0.9731. Effective in-situ surface-enhanced Raman scattering (SERS) studies for Ag nanoparticles decorated graphitic carbon nitride has been carried out and the obtained result shows good sensing performance of the material towards acetaminophen drug. This method opens the possibility of the Nobel metal decorated graphitic carbon nitride for real-time sensing of SERS-based drug products along with the development of high-performance sensing of the target analyte in the future.

Hydrochar (HC) serves as a promising adsorbent to remove the cadmium from aqueous solution due to porous structure. The chemical aging method is an efficient and easy-operated approach to improve the adsorption capacity of HC. In this study, four chemical aging hydrochars (CAHCs) were obtained by using nitric acid (HNO₃) with mass fractions of 5% (N5-HC), 10% (N10-HC), and 15% (N15-HC) to age the pristine HC (N0-HC) and remove the Cd²⁺ from the aqueous solution. The results displayed that the N15-HC adsorption capacity was 19.99 mg g⁻¹ (initial Cd²⁺ concentration was 50 mg L⁻¹), which increased by 7.4 folds compared to N0-HC. After chemical aging, the specific surface area and oxygen-containing functional groups of CAHCs were increased, which contributed to combination with Cd²⁺ by physical adsorption and surface complexation. Moreover, ion exchange also occurred during the adsorption process of Cd²⁺. These findings have important implications for wastewater treatment to transform the forestry waste into a valuable adsorbent for Cd²⁺ removal from water.

To explore a novel strategy for the remediation of soils polluted with Cu and Cd, three strains of plant-growth-promoting rhizobacteria (PGPRs) isolated from contaminated mines and two grass species (perennial ryegrass and tall fescue) were selected in this study. The performance of PGPR strains in metal adsorption, maintaining promotion traits under stress, and ameliorating phytostabilization potential was evaluated. Cd²⁺ exerted a stronger deleterious effect on microbial growth than Cu²⁺, but the opposite occurred for grass seedlings. Adsorption experiment showed that the growing PGPR strains were able to immobilize maximum 79.49% Cu and 81.35% Cd owing to biosorption or bioaccumulation. The strains exhibited the ability to secrete indole-3-acetic acid (IAA) and dissolve phosphorus in the absence and presence of metals, and IAA production was even enhanced in the presence of low Cu²⁺ (5 mg L⁻¹). However, the siderophore-producing ability of the isolates was strongly suppressed under Cu and Cd exposure. Ryegrass was further selected for pot experiments owing to its higher germination rate and tolerance under Cu and Cd stress than fescue. Pot-experiment results revealed that PGPR addition significantly increased the shoot and root biomasses of ryegrass by 11.49%–44.50% and 43.53%–90.29% in soil co-contaminated with 800 mg Cu kg⁻¹ and 30 mg Cd kg⁻¹, respectively. Metal uptake and translocation in inoculated ryegrass significantly decreased owing to the reduced diethylenetriamine pentaacetic acid-extractable metal content and increased residual metal-fraction percentage mediated by PGPR. Interestingly, stress mitigation was observed in these inoculated plants; in particular, their malondialdehyde content and superoxide dismutase activity were even significantly lower than those of ryegrass under normal conditions. Therefore, PGPR could be a promising option to enhance the phytostabilization efficiency of Cu and Cd in heavily polluted soils.